WO2006059729A1

WO2006059729A1 - Method of synthesizing higher-molecular alcohol

Info

Publication number: WO2006059729A1
Application number: PCT/JP2005/022217
Authority: WO
Inventors: Takashi Tsuchida; Shuji Sakuma
Original assignee: Kabushiki Kaisha Sangi
Priority date: 2004-12-03
Filing date: 2005-12-02
Publication date: 2006-06-08
Also published as: JP4903582B2; BRPI0515805B1; RU2007124714A; EP1829851A1; EP1829851B1; EP1829851A4; US8080695B2; KR20070085516A; BRPI0515805A; AU2005310507B2; JPWO2006059729A1; US20070255079A1; KR101113050B1; AU2005310507A1; KR20090009330A; CN101065345A; CA2589125A1; CA2589125C; CN102911010A; CN102911010B

Abstract

A clean process for efficiently producing, from ethanol as a raw material, higher-molecular alcohols having an even number of carbon atoms, such as 1-butanol, hexanol, octanol, and decanol and a mixture of these. The higher-molecular alcohols are yielded from ethanol as a starting material with the aid of a calcium phosphate compound, e.g., hydroxyapatite Ca10(PO4)6(OH)2, tricalcium phosphate Ca3(PO4)2, calcium monohydrogen phosphate CaHPO4·(0-2)H2O, calcium diphosphate Ca2P2O7, octacalcium phosphate Ca8H2(PO4)6·5H2O, tetracalcium phosphate Ca4(PO4)2O, or amorphous calcium phosphate Ca3(PO4)2·nH2O, preferably hydroxyapatite, as a catalyst, the contact time being 0.4 seconds or longer.

Description

Synthesis method of polymer alcohol

Technical field

The present invention relates to a method for producing a polymer alcohol from ethanol using a calcium phosphate catalyst.

Background art

[0002] Butanol (C H OH), Hexanol (C H OH), Octanol (C H OH), Decano

4 9 6 13 8 17

High molecular alcohols such as alcohol (C H OH) are based on propylene, which is currently available in petroleum.

10 21

It is synthesized by the oxo method. In 2004, however, the price of crude oil exceeded $ 50 per barrel, and soaring propylene as a raw material led to high production costs for polymer alcohol, resulting in poor profitability.

[0003] Further, in the case of the oxo method, harmful monoxide and carbon must be used as a raw material in addition to propylene, and since it is a high-pressure reaction and the process is complicated, the production cost is increased. It is a factor. Furthermore, in the oxo method, for example, in the case of butanol synthesis reaction, 2 moles of carbon dioxide, a global warming substance, is generated as a by-product per mole of butanol, which is also preferable from the viewpoint of global environmental conservation. ,.

CH CH = CH (propylene) + 3CO (—carbon oxide) + 2H 0 (water) → C H OH (butano

3 2 2 4 9)) + 2CO (carbon dioxide) …… (1)

2

As a method for synthesizing 1-butanol from ethanol, MgO catalyst ("Dimerisation of ethanol to butanol over solid-base catalysts AS Ndou, N. plint, NJ and oville, Applied catalysis A: General, 251, p. 337-345 ( 2003).) And alkali metal supported zeolite (Z SM-5), Bimolecular Condensation of Ethanol to 1-Butanol Catalyzed by Alka li Cation Zeolites "C. Yang, Z. Meng, J. of Catalysis, 142, p 37-44 (1993).), But is not industrially suitable due to low selectivity.

[0004] In addition, a method for synthesizing 1-butanol using a calcium phosphate catalyst (International Publication W 099/38822) is already disclosed. This synthesis method has a high reaction temperature of 350 to 450 ° C. , 1-butanol selectivity is low, catalyst characteristics deteriorate quickly There were problems that had to be done frequently, reduced durability of the equipment, and increased fuel costs for maintaining the reaction temperature.

[0005] Patent Document 1: International Publication No. W099 / 38822

Non-Patent Document 2: "Bimolecular". Special Reference 1: Dimensation of ethanol to butanol over solid-base catalysts AS N dou, N. plint, NJ Coville, Applied catalysis A: General, 251, p. 337-345 (2003). Condensation of Ethanol to 1- Butanol Catalyzed by Alk ali Cation Zeolites "C. Yang, Z. Meng, J. of Catalysis, 142, p. 37—44 (1993).

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention provides a production method for efficiently collecting high-molecular alcohols having an even number of carbon atoms such as 1-butanol, hexanol, octanol, decanol and mixtures thereof using ethanol as a raw material in an efficient and clean process. The issue is to provide. Means for solving the problem

[0007] Ethanol, which is a starting material for the present application process, is synthesized by converting sugars, such as sugar cane and beet, that are obtained with a fermentation method. In recent years, technology for synthesizing ethanol from biomass, which is agricultural and forestry waste, has been established, and it is expected that the production of ethanol will increase dramatically in the future. As a result, ethanol production costs are expected to fall to a level comparable to that of crude oil. In fact, in Brazil, which is a developed country of ethanol, ethanol production costs are said to be around 10 yen Z liter, which is comparable to or cheaper than international crude oil prices. Therefore, by adopting the process of this application, we can obtain a polymer alcohol that is cheaper than the oxo method.

[0008] In the polymer alcohol synthesis method of the present application, the raw material is only ethanol, and the reaction proceeds easily at normal pressure. The only byproduct of the polymer alcohol synthesis reaction is water (see the following reaction formula). Therefore, this process is an atmospheric pressure reaction that does not require the use of toxic substances as in the oxo method, so it is possible to reduce plant safety management costs and plant construction costs, and to reduce the production cost of polymer alcohol. It is. The oxo method generates carbon dioxide as a by-product, but this reaction is a clean process that is friendly to the global environment because the only by-product is water. The main polymer alcohol synthesis reaction The reaction formula of the process is shown below.

2C H OH (ethanol) → C H OH (1-butanol) + H 0 (water) …… (2)

2 5 4 9 2

3C H OH (ethanol) → C H OH (hexanol) + 2H 0 (water) …… (3)

2 5 6 13 2

4C H OH (ethanol) → C H OH (octanol) + 3H 0 (water) …… (4)

2 5 8 17 2

5C H OH (ethanol) → C H OH (decanol) + 4H 0 (water) …… (5)

2 5 10 21 2

[0009] From the ratio of the amount of these polymer alcohols synthesized, the polymer alcohol synthesis reaction from ethanol with a calcium phosphate catalyst is considered to be a sequential reaction of ethanol. Therefore, when a polymer alcohol having an even number of carbon atoms such as butanol having 4 carbon atoms, hexanol having 6 carbon atoms, octanol having 8 carbon atoms, or decanol having 10 carbon atoms is synthesized from ethanol having 2 carbon atoms. Think. Assuming that the polymer alcohol is synthesized as a result of the sequential reaction of ethanol, the reactions (3) to (5) are represented by the following formulas (6) to (8).

C H ΟΗ (1-butanol) + C H OH (ethanol) → C H OH (hexanol) + H

4 9 2 5 6 13 2

. (Wed) …… (6)

C H OH (Hexanol) + C H OH (Ethanol) → C H OH (Otanol) + H

6 13 2 5 8 17 2

. (Wed) …… (7)

C H OH (Otano no Nore) + C H OH (Etano Nore) → C H OH (Decano Nore) + H 0

8 17 2 5 10 21 2

(Wed) …… (8)

[0010] As a result of intensive studies on the influence of the contact time in the ethanol transfer reaction, the present inventors have made contact with ethanol with a calcium phosphate catalyst at a contact time of 0.4 seconds or longer, thereby increasing the above-mentioned high value. We found that molecular alcohols can be synthesized with high selectivity. In general, the relationship between the contact time and the reaction product selectivity in the catalytic reaction shows that the selectivity of a single substance decreases due to the polycondensation of raw materials and the occurrence of multiple reactions as the contact time increases. In contrast, by increasing the contact time at an arbitrary temperature to 0.4 seconds or longer, it was possible to increase the selectivity of the polymer alcohol.

[0011] Regarding the relationship between the contact time and the abundance ratio of the polymer alcohol, the sequential reaction of ethanol progressed as the contact time became longer, and alcohol with a higher molecular weight was synthesized. This is considered to be a reaction intermediate in the ethanol transfer reaction using these polymer alcohol power hydroxyapatite catalysts. Brief Description of Drawings

[0012] FIG. 1 is a graph showing the relationship between the contact time in Table 1 and the polymer alcohol selectivity.

[FIG. 2] FIG. 2 is an enlarged graph of the contact time of 0.0 to 1.0 seconds in FIG.

FIG. 3 is a graph showing the results of GC-MS analysis.

FIG. 4 is a graph showing the relationship between reaction temperature and 1-butanol selectivity.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] Calcium phosphate catalysts include hydroxyapatite Ca (PO) (OH), phosphoric acid tricalcium

10 4 6 2

Sim Ca (PO), calcium monohydrogen phosphate CaHPO. (0-2) H 0, dicalcium phosphate Ca

3 4 2 4 2 2

P 0, 8 calcium phosphate Ca H (PO) 5PO 0, 4 calcium phosphate Ca (PO) 0, amorphous

2 7 8 2 4 6 2 4 4 2 Presence of calcium phosphate Ca (PO) · ηΗ 0 etc. is known. Hydroxyapatite

3 4 2 2

Usually, it is shown by the above stoichiometric composition, but the characteristic is that it can take an apatite structure even if the stoichiometric composition is not satisfied. Hydroxyapatite having such a non-stoichiometric composition is Ca (HPO) (PO) (OH) · ηΗ Ο {0 <Ζ≤ 1, η = 0 ~ 2.5}

10-Ζ 4 Z 4 6-Z 2-Z 2

. The amorphous calcium phosphate catalyst is a halo calcium phosphate catalyst that is halo in X-ray diffraction.

The present invention efficiently produces the above-mentioned polymer alcohol by using these calcium phosphate catalysts and optimizing the reaction conditions, that is, the contact time and the reaction temperature.

[0014] In the present invention, a method for producing a calcium phosphate compound used as a catalyst is not particularly limited, and includes a dry solid phase reaction method, a wet precipitation reaction method, a wet solid phase reaction method, a hydrothermal synthesis method, and the like. It can be synthesized by a known synthesis method.

For example, when synthesizing hydroxyapatite, a calcium salt solution and a phosphate solution of a predetermined concentration are dropped into a stirring aqueous solution while adjusting the pH, and the precipitated product is collected, washed, Dry, pulverize, and calcinate as necessary to obtain a catalyst raw material. The calcium salt used is Ca (OH), Ca (NO 3) power. The phosphate is preferably ammonium phosphate.

2 3 2

The CaZP molar ratio of hydroxyapatite can be controlled by controlling the preparation ratio of the raw material salt and the synthesis conditions. For example, the aqueous solution can be made basic with aqueous ammonia during synthesis. When adjusted, the CaZP molar ratio increases, and when the aqueous solution is adjusted to neutral or weakly acidic with dilute acid, the CaZP molar ratio decreases. It can also be obtained by mixing a calcium phosphate catalyst with a known CaZP molar ratio and then firing in a moisture atmosphere.

[0015] In the case of using nodyloxyapatite as a catalyst, the CaZP molar ratio is adjusted to 1.4 to 1.8, preferably 1.5 to 1.7. Select the atmosphere. At this time, the specific surface area of the catalyst is desirably 2 m ² / g or more.

[0016] Control of the CaZP molar ratio in a calcium phosphate catalyst is to control the type and distribution density of solid acid points and solid base points which are active sites on the catalyst surface. Here, the strength and amount of the acid point and base point are NH-TPD (Temparature Programmed Deso

Three

(rption: thermal desorption method) and CO-TPD, pyridine adsorption method, indicator method, etc.

2

can do. As a method for controlling the acidity and basicity of the catalyst surface, it is generally known that metal is supported.

[0017] For example, supporting a dehydrogenation-promoting metal typified by Ni, Zn, Cu, Pd or Pt on nodoxyapatite has the same effect as an increase in the Ca / P molar ratio, that is, a solid salt. Increased basicity. In the case of nodyloxyapatite, supporting a dehydration-promoting metal typified by A1 has the same effect as a decrease in the CaZP molar ratio, that is, increased calorie of solid acid characteristics. Therefore, instead of changing the CaZP molar ratio, the solid acid Z basicity on the surface of the hydroxyapatite catalyst can be changed by supporting a powerful metal. A plurality of metals may be co-supported for synergistic effect or durability improvement. Coexisting supported metals include, for example, Zn, Co, Cr, Mo, W, Fe, Ni, Cu, Mn, Ti, V, Ga, Zr, Nb, Cd, In, Sn, Sb, Pb, La, Ce, Transition metals such as Eu and Y, or noble metals such as Pt, Pd, Rh, Au, Ir, Ru, and Ag, and alkali or alkaline earth metals such as Ba, Na, K, Li, Sr, Ca, Mg, Cs, and Rb In some cases, an oxide or sulfide of these metals can also be used. These substances are used in the range of 0.05 to 70 mol% with respect to calcium of the calcium phosphate catalyst.

[0018] In the present invention, when synthesizing a polymer alcohol and a mixture thereof using ethanol as a raw material, the calcium phosphate catalyst used, the acid on the catalyst surface, Basic control (for example, calcium phosphate catalyst) (CaZP molar ratio) and reaction conditions (contact time, reaction temperature, pressure, etc.) are selected as appropriate.

[0019] The calcium phosphate-based catalyst prepared as described above can be used in any form such as granules and powders, and if necessary, formed into an arbitrary shape such as spheres, pellets, and honeycombs, and then dried. It can also be used after firing. The calcium phosphate catalyst may be supported on a carrier such as conventional alumina, silica, alumina silica, zeolite, clay mineral, etc., which are well known to those skilled in the art. Firing is performed at 200 ° C to 1200 ° C, preferably 400 ° C to 700 ° C.

[0020] The reaction temperature suitable for synthesizing the polymer alcohol by bringing ethanol into contact with the calcium phosphate catalyst is usually selected from the range of 150 ° C to 450 ° C, more preferably 200 ° C. ° C to 350 ° C is desirable. Even if the temperature is below 150 ° C, there is a means to keep the selectivity of the polymer alcohol high. Since the ethanol conversion rate is low, the yield is low and the economy is poor. At 450 ° C or higher, the ethanol conversion rate increases. The polymer alcohol selectivity decreases, the number of unnecessary reaction products increases, and new disposal problems arise. It gets worse.

[0021] The contact time of the present application is usually 0.4 seconds or more. Preferably it is 0.6 seconds or longer. Shorter than 4 seconds, the polymer alcohol selectivity is low and the ethanol conversion rate is also low, resulting in a low synthesis yield and poor economic efficiency. If the reaction is performed at a low temperature, a batch reactor corresponding to an infinite contact time can be used to increase the ethanol conversion. At higher temperatures, longer contact times increase other reactions and lower polymer alcohol selectivity.

[0022] Ethanol power The reaction for synthesizing the polymer alcohol is an exothermic reaction. Therefore, when a high yield of high molecular alcohol is targeted, the temperature rise inside the reaction tower due to the heat of reaction becomes significant. As a result, problems such as a decrease in polymer alcohol selectivity due to the occurrence of another reaction such as an ethanol decomposition reaction, deterioration of the catalyst due to an increase in catalyst temperature, and a decrease in durability of the reactor occur. Therefore, in the case of a reaction for synthesizing a polymer alcohol from ethanol, it is better for the industrial industry to target the selectivity, rather than aiming at a high yield. However, this does not apply if a system for removing reaction heat is introduced inside the reaction tower. [0023] Ethanol can be efficiently reacted by contacting it with a catalyst directly in the gas phase or in the presence of an inert carrier gas such as nitrogen or helium. At this time, in order to maintain the catalyst activity, a reactive gas such as hydrogen or hydrocarbon may be accompanied in the carrier gas.

[0024] As the reaction mode in the reaction tower, it can be carried out at normal pressure or under pressure by any method of batch system, continuous system, fixed bed, moving bed, fluidized bed or slurry bed. In the case of a polymer alcohol synthesis reaction, carbon may be deposited on the catalyst surface over a long period of use, leading to a decrease in ethanol conversion and a heterogeneous reaction. In that case, regeneration treatment is periodically performed by heating the catalyst in an oxygen atmosphere. Thereby, the activity of the catalyst can be recovered. Therefore, in the case of reaction conditions with a large amount of carbon deposition on the catalyst, a plant based on the above-described method incorporating a catalyst regeneration treatment apparatus is effective.

[0025] The polymer alcohol thus obtained is conventionally used! /, And is separated and purified using a separation and purification method such as rectification, microporous membrane separation, extraction, and adsorption method. be able to.

[0026] The catalyst was synthesized as follows. The crystal structure of the obtained powder is a powder X-ray diffractometer M18XHF ²² manufactured by MatsuScience Co., Ltd., SA3100 of COLTER Co., Ltd. is used to measure the specific surface area, and Rigaku Electric Industries Co., Ltd. ) RIX 1000 fluorescent X-ray analyzer was used.

[Example 1] Preparation of catalyst

225. 2 g of calcium nitrate: Ca (NO) · 4Η に dissolved in 5.0 liters of distilled water, and

3 2 2

78. 87g of ammonium phosphate: (ΝΗ) A solution of ΗΡΟ in 3.0 liters of distilled water,

4 2 4

Drop it in ammonia water adjusted to pH 9 to L 1 under a nitrogen atmosphere and stir for 1 day. Thereafter, filtration, washing with water and drying were carried out, and ion-exchanged water was added to the obtained powder and ground with a ball mill for 48 hours. The resulting slurry was aged and dried at 140 ° C. in an oven. This powder was calcined in the atmosphere at 600 ° C. for 2 hours to obtain a powdery catalyst composition having a CaZP molar ratio of 1.64.

[0028] [Example 2] Evaluation of catalyst characteristics

The reactor used was a fixed bed gas flow type catalytic reactor. 14-26 mess of powder catalyst Molded into a tablet. This tablet was filled into the reaction tube in an amount corresponding to the contact time, and as a pretreatment, a heat dehydration treatment was performed at 500 ° C. for 30 minutes in a carrier gas (l% ArZHe base; flow rate 112 ml / min) atmosphere. After completion of the pretreatment, the reaction was carried out at normal pressure under the conditions of an ethanol concentration of 16 vol% and a carrier gas flow rate of 112 ml / min (total flow rate of 134 ml / min). In the case of the polymer alcohol synthesis test, the reaction temperature was fixed at 300 ° C., and the contact time was in the range of 0.02 seconds to 29.4 seconds. In the optimization test of 1-butanol synthesis conditions, the contact time was fixed at 1.0 seconds, the ethanol concentration was 8.1%, and the reaction temperature was in the range of 150 to 500 ° C.

[0029] A gas chromatograph mass spectrometer (GC—MS) was used to identify the reaction gas components, and a gas chromatograph (GC) (detector: FI) was used to measure the ethanol conversion rate and synthesis gas selectivity. D) was used. Here, to calculate the selectivity of raw materials ethanol, butanol, hexanol, octanol, decanolole [force of 0.70, 0.85, 0.90, 0.93, 0.94, respectively] A coefficient was used.

[0030] Ethanol conversion rate (%) = (1-ethanol carbon moles Z total carbon moles) 100

1-butanol selectivity (%) = (1-butanol carbon moles Z total carbon moles) 100

* The calculation of hexanol, octanol and decanol selectivity is the same as for 1-butanol. Polymer alcohol selectivity (%) = 1-butanol selectivity + hexanol selectivity + octanol selectivity + decanol selectivity

[0031] The test results are shown in Table 1, Fig. 1 and Fig. 2 (enlarged between contact times of 0.0 to 1.0 seconds in Fig. 1).

[0032] [Table 1]

Table 1 shows the relationship between the contact time and the polymer alcohol selectivity when an ethanol transfer test was conducted using a hydroxyapatite catalyst at an ethanol concentration of 16% and a reaction temperature of 300 ° C. [0034] The 1-butanol selectivity reached its maximum value at a contact time of 1.34 seconds, and decreased when the contact time was longer. The selectivity of hexanol, octanol, and decanol decreased in this order, and each contact rate increased with increasing contact time up to a contact time of 29.4 seconds.

[0035] The polymer alcohol selectivity is very small, 2.4% at a contact time of 0.02 seconds. Force increases rapidly with increasing contact time, and exceeds 60% at a contact time of 0.4 seconds. It was. Furthermore, when the contact time was 0.6 seconds or more, the polymer alcohol selectivity was a very high value of 70% or more, which is advantageous for industrial applications.

[0036] [Example 3] Example of analysis by gas chromatograph mass spectrometer (GC—MS)

The ethanol conversion test was conducted using an idroxyapatite catalyst at an ethanol concentration of 16%, a contact time of 1.78 seconds, and a reaction temperature of 300 ° C, and analyzed by GC-MS. Figure 3 shows the results.

[0037] Retention time 8.5-min for 1-butanol, 13-14 min for hexanol (iso and normal), 17-18 min for octanol (iso and normal), 20- At 22 minutes, a peak of depressor (iso and normal) was confirmed.

From this result, it is clear that a polymer alcohol having an even number of carbon atoms and an even number is selectively synthesized.

[0038] [Example 4] Evaluation of reaction temperature and 1-butanol selectivity

The ethanol conversion test was conducted using ethanol and idroxyapatite catalyst at an ethanol concentration of 8.1% and a contact time of 1.0 seconds. For comparison, an ethanol conversion test was conducted with a contact time of only 0.3 seconds. The results are shown in Fig. 4.

[0039] As a result of comparing the 1-butanol synthesis characteristics of contact time 1.0 seconds and 0.3 seconds, the 1-butanol selectivity of contact time 1.0 seconds is 1-butanol selectivity of contact time 0.3 seconds. Compared with the reaction temperature at the maximum value, the selectivity is about 12% higher, and when the contact time is 1.0 second, the contact time is about 75 ° C lower than the contact time of 0.3 second. ing.

Industrial applicability

[0040] The catalyst according to the present method is inexpensive and easy to manufacture and is stable to the reaction and regeneration treatment. By selecting the reaction temperature and contact time, the ethanol power can be increased efficiently. Molecular alcohols can be obtained.

Claims

The scope of the claims

[1] A method for synthesizing a polymer alcohol having an even number of carbon power and an even number, characterized in that ethanol is brought into contact with calcium phosphate at a contact time of 0.4 seconds or longer.

[2] A method for synthesizing 1-butanol, characterized by contacting ethanol with calcium phosphate at a contact time of 0.4 seconds or longer and at 200 ° C to 350 ° C.

[3] The method for synthesizing a high molecular alcohol according to [1], wherein the calcium phosphate is hydroxyapatite.

[4] The method for synthesizing 1-butanol according to claim 2, wherein the calcium phosphate is hydroxyapatite.